An efficient method for the preparation of various 2-substituted-1,4-benzodioxanes by CuBr-catalyzed tandem reactions of 2-((o-iodophenoxy)methyl)oxiranes with phenols has been developed. The reaction involves the ring-opening process of 2-((2-iodophenoxy)methyl)oxirane followed by an intramolecular C–O cross coupling cyclization.